Heck reactions of alkenes with aryl iodides and aryl bromides: Rate-determining steps deduced from a comparative kinetic study of competing and noncompeting reactions

Schmidt, Alexander F.; Al-Halaiqa, A.; Смирнов, В. В.

doi:10.1134/s0023158407050175

Cited by 25 publications

(24 citation statements)

References 65 publications

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“…There is a certain misunderstanding about the Hammett plots obtained by differential selectivities (in competitive reactions), and the activity (in non-competitive reactions) may be different because the stages determining the selectivity and activity may be different (for further details, see ref. 102). To demonstrate this distinction, we will use the most common example from section 2.1.3.…”

Section: Using Hammett Plotsmentioning

confidence: 99%

Differential selectivity measurements and competitive reaction methods as effective means for mechanistic studies of complex catalytic reactions

Schmidt

Kurokhtina

Larina

2014

Catal. Sci. Technol.

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Section: Using Hammett Plotsmentioning

confidence: 99%

Differential selectivity measurements and competitive reaction methods as effective means for mechanistic studies of complex catalytic reactions

Schmidt

Kurokhtina

Larina

2014

Catal. Sci. Technol.

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“…An important role in answering the question con cerning homogeneity or "heterogeneity" of the pro cesses considered above was played by the investiga tions of competitive Heck reaction [142][143][144] and Suzuki-Miyaura coupling [139] in respect of selectiv ity, which employed the creation of artificial conjuga tion nodes at various stages of the process involving the expected active species. The problem of the nature of active centers is not always simple to solve even in the case of homogeneous reactions not involving microheterogeneous species.…”

Section: Arylation Of Olefins Via the Heck (Heck-mizoroki) Reaction Imentioning

confidence: 99%

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

Темкин

2012

Kinet Catal

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The state of the art in the theory of routes for multi route reactions in the homogeneous catalysis with metal complexes is reviewed. Key problems and the possible approaches to their solution based on the Horiuti-Temkin theory of steady state reactions, which are useful in constructing the kinetic algebraic mod els of multi route processes, are discussed. A classification of the mechanisms of real processes involved in the homogeneous catalysis with metal complexes is presented. The chain mechanisms of catalytic processes, conjugated and associated reactions, and critical phenomena in the dynamics of homogeneous reactions are considered.

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“…This mechanism has not been proved in all details, and especially, the ratedetermining step has not been identified unequivocally in all cases. Frequently, the oxidative addition has been assumed to be rate determining; however, in certain cases, it has been doubted 2) or even disproved experimentally [11,18]. 8…”

Section: The Mechanismmentioning

confidence: 99%

“…However, all ring sizes from three-to nine-membered are attainable, either by exo-trig cyclizations for three-(Scheme 8.10) to nine-membered rings or by endo-trig cyclizations for six-to nine-membered rings (Scheme 8.11). Applications toward the construction of larger rings (sizes [13][14][15][16][17][18][19][20][21][22][23][24] …”

Section: Structural Requirements In Intramolecular Cyclizationsmentioning

confidence: 99%

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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Heck reactions of alkenes with aryl iodides and aryl bromides: Rate-determining steps deduced from a comparative kinetic study of competing and noncompeting reactions

Cited by 25 publications

References 65 publications

Differential selectivity measurements and competitive reaction methods as effective means for mechanistic studies of complex catalytic reactions

Differential selectivity measurements and competitive reaction methods as effective means for mechanistic studies of complex catalytic reactions

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

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